Photographic products and processes employing metal complexable nondiffusible azo dye-releasing compounds

ABSTRACT

Photographic elements, diffusion transfer assemblages and processes are described which employ a novel nondiffusible compound having a releasable azo dye moiety. The compound has the formula: ##STR1## wherein: G is a metal chelating group (or a salt or hydrolyzable precursor thereof) or a group which together with a ##STR2##  is CAR (bonded through the oxygen); G 1  is a hydroxy group (or a salt or hydrolyzable precursor thereof); 
     Z is an electron withdrawing group; 
     Z&#39; is alkyl, aryl or N(R) 2  (R being H, alkyl or aryl); 
     CAR is a ballasted carrier moiety; and 
     t is 0 or 1. 
     The dye can be transferred imagewise to an image-receiving layer where it can be contacted with metal ions to form a metal-complexed azo dye transfer image of excellent stability. The retained dye image in the photographic element can also be bleached, fixed and metallized to form a color transparency or a motion picture film.

This is a division of application Ser. No. 892,561, filed Apr. 3, 1978.

This invention relates to photography and more particularly to colordiffusion transfer photography employing certain nondiffusible azodye-releasing compounds which, as a function of development of a silverhalide emulsion layer, release a diffusible, metallizable azo dye.Highly stable metal complexes of this dye are formed in animage-receiving layer.

Azo dye developers containing metallizable groups are disclosed in U.S.Pat. Nos. 3,081,167; 3,196,014; 3,299,041; 3,453,107; 3,563,739;3,544,545, 3,551,406 and 4,014,700. Since it is a reactive species,however, the developer moiety of such dye developers is capable ofdeveloping any exposed silver halide emulsion layer with which it comesinto contact, rather than just developing the adjacent silver halideemulsion with which it is associated. Unwanted wrong-layer development,therefore, can occur in dye developer systems which results inundesirable interimage effects. Accordingly, it is desirable to providean improved transfer system in which the attachment of the dye to a"reactive" moiety, such as a developer moiety, is avoided, so that suchdye can diffuse throughout the photographic film unit without becomingimmobilized in undesired areas.

In U.S. published patent application Ser. No. B351,673, published Jan.28, 1975, nondiffusible dye releasing compounds are disclosed. Among thevarious dye moieties disclosed which can be released are "metalcomplexed dyes". No specific structures are shown, however.

The April 1977 edition of Research Disclosure, pages 32 through 39,discloses various nondiffusible dye-releasing compounds and variousmetallized azo dye fragments. Such premetallized dyes are large molculeswhich diffuse more slowly than unmetallized dyes, resulting in longaccess times for image formation in color image transfer systems. Thespecific compounds employed in the instant invention, however, are notdisclosed.

In accordance with our invention, we have provided improveddye-releasing compounds containing chelating dye moieties, so that thedye which is released imagewise during processing can diffuse to animage-receiving layer containing metal ions to form a metal-complexed,dye transfer image having better hues, rapid diffusion rates and shorteraccess times than those of the prior art, as well as good stability toheat, light and chemical reagents. Many of the dyes of the presentinvention, when chelated by metal ions such as nickel(II) ions, havegood yellow hue with minimal unwanted absorption outside the blue regionof the spectrum. They have superior stability to fading by light in avariety of environments.

A photographic element in accordance with the invention comprises asupport having thereon at least one photosensitive silver halideemulsion layer having associated therewith a nondiffusible compoundhaving at least one diffusible azo dye moiety, said compound having theformula: ##STR3## wherein:

G is a metal chelating group (any group which will donate a pair ofelectrons to a metal ion), a salt thereof (such as an alkali metal salt,a quaternary ammonium salt, etc) or a hydrolyzable precursor thereof(e.g., a hydrolyzable acyl or ester group); or a group which togetherwith a ##STR4## is CAR, said CAR being bonded to the benzene ringthrough the oxygen of said ##STR5##

G¹ is a hydroxy group or a salt thereof (such as a sodium salt, atetramethylammonium salt, etc), or a hydrolyzable precursor thereof;

Z is an electron withdrawing group having the formula --CON(R)₂, --SO₂N(R)₂, --COOR, --CN, SO₂ R', or --COR', wherein R' is an alkyl(including substituted alkyl) group of 1 to 8 carbon atoms, such asmethyl, ethyl, isopropyl, 2-sulfamoylethyl, 2-hydroxyethyl, butyl andthe like; or an aryl (including substituted aryl) group of 6 to 10carbon atoms, such as phenyl, m-hydroxyphenyl, p-sulfamoylphenyl, etc;and each R is H or R';

Z' is an alkyl (including substituted alkyl) group of 1 to 8 carbonatoms, such as methyl, ethyl, isopropyl, 2-sulfamoylethyl,2-hydroxyethyl, butyl and the like; or an aryl (including substitutedaryl) group of 6 to 10 carbon atoms, such as phenyl, m-hydroxyphenyl,p-sulfamoylphenyl, etc; and each R is H or R';

Z' is an alkyl (including substituted alkyl) group of 1 to 8 carbonatoms, such as methyl, ethyl, isopropyl, 2-sulfamoylethyl,2-hydroxyethyl, butyl and the like; an aryl (including substituted aryl)group of 6 to 10 carbon atoms, such as phenyl, m-hydroxyphenyl,p-sulfamoylphenyl, etc; or N(R)₂, wherein R is defined as above;

CAR represents a ballasted carrier moiety which is capable of releasingsaid diffusible azo dye under alkaline conditions such as, for example,as a function (either direct or inverse) of development of the silverhalide emulsion layer; and

t is an integer of 0 or 1, with the proviso that the compound containsat least one but not more than two CAR groups.

For example, G may be hydroxy; amino; carboxy; sulfonamide; sulfamoyl; afused nitrogen-containing ring, such as a quinoline ring; or ahydrolyzable ester group having the formula --OCOR¹, --OCOOR¹, or--COOR¹, wherein R¹ is an alkyl (including substituted alkyl) grouphaving 1 to about 8 carbon atoms, such as methyl, ethyl, isopropyl,2-sulfamoylethyl, 2-hydroxyethyl, butyl and the like, or an aryl(including substituted aryl) group having 6 to about 12 carbon atoms,such as phenyl, p-methoxyphenyl, p-sulfamoylphenyl, etc.

Examples of hydrolyzable precursors of a hydroxy group for G¹ include,for example, an acyloxy group having the formula --OCOR¹, --OCOOR¹ or--OCON(R¹)₂, wherein each R¹ is an alkyl group having 1 to about 8carbon atoms, such as methyl, ethyl, isopropyl, 2-sulfamoylethyl,2-hydroxyethyl, butyl and the like, or an aryl group having 6 to about12 carbon atoms, such as phenyl, p-methoxyphenyl, p-sulfamoylphenyl,etc.

Other substituents may also be present on the benzene ring shown in theformula above, such as alkyl of 1 to 6 carbon atoms, alkoxy, amino,halogens, acetamido, carbamoyl, alkoxycarbonyl, solubilizing groups suchas sulfonamido, sulfamoyl, carboxy, sulfo, hydrolyzable precursorsthereof, etc. In a preferred embodiment of the invention, t is 1, G isOH, G¹ is OH, Z is --CON(R)₂ and Z' is an alkyl group of 1 to 8 carbonatoms.

In another preferred embodiment of the invention, CAR may have attachedthereto two azo dye moieties of the formula above, in which case two dyemoieties can be released from one CAR moiety.

When hydrolyzable precursors for G and G¹ of the dye moiety in the aboveformula are employed, the absorption spectrum of the azo dye is shiftedto shorter wavelengths. "Shifted dyes" of this type absorb light outsidethe range to which the associated silver halide layer is sensitive. Insome cases, the absorption spectrum of the unmetallized azo dye ligandis substantially shifted to shorted wavelengths at neutral pH (e.g., 5to 8).

There is great latitude in selecting a CAR moiety which is attached tothe azo dye-releasing compounds described above. Depending upon thenature of the ballasted carrier selected, various groups may be neededto attach or link the carrier moiety to the dye. Such linking groups areconsidered to be a part of the CAR moiety in the above definition. Itshould also be noted that when the dye moiety is released from thecompound in an image transfer system, cleavage may take place in such aposition that part or all of a linking group, if one is present, andeven part of the ballasted moiety may be transferred to theimage-receiving layer along with the dye moiety. In any event, the dyenucleus as shown above can be thought of as the "minimum" which istransferred.

CAR moieties useful in the invention are described in U.S. Pat. Nos.3,227,550; 3,628,952; 3,227,552; and 3,844,785 (dye released bychromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dyereleased by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No.3,728,113 (dye released from a hydroquinonylmethyl quaternary salt);U.S. Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release);and U.S. Pat. Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607;British Pat. No. 1,464,104; Research Disclosure 14447, April 1976; andU.S. Pat. No. 4,139,379, issued Feb. 13, 1979 of Chasman et al (dyereleased by miscellaneous mechanisms), the disclosures of which arehereby incorporated by reference.

In a further preferred embodiment of the invention, the ballastedcarrier moiety or CAR, as described above, may be represented by thefollowing formula:

    (Ballast--Carrier--Link)--

wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety(see "The theory of the Photographic Process", by C. E. K. Mees and T.H. James, Third Edition, 1966, pages 282 to 283), e.g., moietiescontaining atoms according to the following configuration:

    a(--═C).sub.b --

wherein:

b is a positive integer of 1 to 2; and

a represents the radicals OH, SH, NH--, or hydrolyzable precursorsthereof; and

(c) Link represents a group which, upon oxidation of said Carriermoiety, is capable of being hydrolytically cleaved to release thediffusible azo dye. For example, Link may be the following groups:##STR6## wherein * represents the position of attachment to the Carrier.

The nature of the Ballast group in the above formula is not critical aslong as it confers nondiffusibility to the compound. Typical Ballastgroups include long-chain alkyl radicals linked directly or indirectlyto the compound as well as aromatic radicals of the benzene andnaphthalene series indirectly attached or fused directly to the ring,etc. Useful Ballast groups generally have at least 8 carbon atoms suchas substituted or unsubstituted alkyl groups of 8 to 22 carbon atoms, acarbamoyl radical having 8 to 30 carbon atoms such as --CONH(CH₂)₄--O--C₆ H₃ (C₅ H₁₁)₂, --CON(C₁₂ H₂₅)₂, etc, a keto radical having 8 to30 carbon atoms such as --CO--C₁₇ H₃₅, --CO--C₆ H₄ (t--C₁₂ H₂₅), etc.

For specific examples of Ballast-Carrier-Link moieties useful as the CARmoiety in this invention, reference is made to the November 1976 editionof Research Disclosure, pages 68 through 74, and the April 1977 editionof Research Disclosure, pages 32 through 39, the disclosures of whichare hereby incorporated by reference.

In a high preferred embodiment of the invention, the ballasted carriermoiety or CAR in the above formulas is a group having the formula:##STR7## wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration (e.g., simple organic groups or polymeric groups) as torender the compound nondiffusible in a photographic element duringdevelopment in an alkaline processing composition;

(b) D is OR² or NHR³ wherein R² is hydrogen or a hydrolyzable moiety andR³ is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22carbon atoms such as methyl, ethyl, hydroxyethyl, propyl, butyl,secondary butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclobutyl,4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl,benzyl, phenethyl, etc. (where R³ is an alkyl group of greater than 8carbon atoms, it can serve as a partial or sole Ballast);

(c) Y represents the atoms necessary to complete a benzene nucleus, anaphthalene nucleus, or a 5 to 7 membered heterocyclic ring such aspyrazolone, pyrimidine, etc;

(d) j is a positive integer of 1 to 2 and is 2 when D is OR² or NHR³when R³ is hydrogen or an alkyl group of less than 8 carbon atoms; and

(e) L is a linking group which is [X--(NR⁴ --J)_(q) ]_(m) -- orX--J--NR⁴ --wherein:

(i) X represents a bivalent linking group of the formula --R⁵ --L'_(n)--R ⁵ _(p) -- where each R⁵ can be the same or different and eachrepresents an alkylene radical having 1 to about 8 carbon atoms, such asmethylene, hexylene and the like; a phenylene radical; or a substitutedphenylene radical having 6 to about 9 carbon atoms, such as methoxyphenylene;

(ii) L' represent a bivalent radical selected from oxy, imino, carbonyl,carboxamido, carbamoyl, sulfonamido, ureylene, sulfamoyl, sulfinyl orsulfonyl;

(iii) n is an integer of 0 or 1,

(iv) p is 1 when n equals 1 and p is 1 or 0 when n equals 0, providedthat when p is 1 the carbon content of the sum of both R⁵ radicals doesnot exceed 14 carbon atoms;

(v) R⁴ represents a hydrogen atom, or an alkyl radical having 1 to about6 carbon atoms;

(vi) J represents a bivalent radical selected from sulfonyl or carbonyl;

(vii) q represents an integer of 0 or 1; and

(viii) m represents an integer of 0, 1 or 2.

Especially good results are obtained in the above formula when D is OH,j is 2, and Y is a naphthalene nucleus.

Examples of the CAR moiety in this highly preferred embodiment aredisclosed in U.S. published patent application Ser. No. B351,673; U.S.Pat. No. 3,928,312; French Pat. No. 2,284,140; and German Pat. Nos.2,406,664; 2,613,005; and 2,505,248, the disclosures of which are herebyincorporated by reference, and include the following: ##STR8##

In another highly preferred embodiment of the invention, the ballastedcarrier moiety or CAR in the above formulas is such that the diffusibleazo dye is released as an inverse function of development of the silverhalide emulsion layer under alkaline conditions. This is ordinarilyreferred to as positive-working dye-release chemistry. In one of theseembodiments, the ballasted carrier moiety or CAR in the above formulasmay be a group having the formula: ##STR9## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W² represents at least the atoms necessary to complete a benzene nucleus(including various substituents thereon); and

R⁷ is an alkyl (including substituted alkyl) radical having 1 to about 4carbon atoms.

Examples of the CAR moiety in this formula I include the following:##STR10##

In a second embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR11## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W¹ represents at least the atoms necessary to complete a quinone nucleus(including various substituents thereon);

r is a positive integer of 1 or 2;

R⁶ is an alkyl (including substituted alkyl) radical having 1 to about40 carbon atoms or an aryl (including substituted aryl) radical having 6to about 40 carbon atoms; and

k is a positive integer of 1 to 2 and is 2 when R⁶ is a radical of lessthan 8 carbon atoms.

Examples of the CAR moiety in this formula II include the following:##STR12##

In using the compounds in formulas I and II above, they are employed ina photographic element similar to the other nondiffusible dye-releasersdescribed previously. Upon reduction of the compound as a function ofsilver halide development under alkaline conditions, the metallizableazo dye is released. In this embodiment, conventional negative-workingsilver halide emulsions, as well as direct-positive emulsions, can beemployed. For further details concerning these particular CAR moieties,including synthesis details, reference, is made to U.S. Pat. No.4,139,379 of Chasman et al, issued Feb. 13, 1979, the disclosure ofwhich is hereby incorporated by reference.

In a third embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR13## wherein:

Ballast, W² and R⁷ are as defined for formula I above.

Examples of the CAR moiety in this formula III include the following:##STR14##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. commonly assigned copendingapplication Ser. No. 534,966 of Hinshaw et al, filed Dec. 20, 1974, thedisclosure of which is hereby incorporated by reference.

In a fourth embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR15## wherein:

Ballast, r, R⁶ and k are as defined for formula II above;

W² is as defined for formula I above; and

K is OH or a hydrolyzable precursor thereof.

Examples of the CAR moiety in this formula IV include the following:##STR16##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 3,980,479 ofFields et al, issued Sept. 14, 1976, the disclosure of which is herebyincorporated by reference.

A bivalent linking group, e.g., L or X as defined above, may be used, ifdesired, to link the CAR moiety described in formulas I through IV aboveto the dye moiety previously described.

Other examples of CAR include the following: ##STR17##

Representative compounds included within the scope of the inventioninclude the following: ##STR18##

A process for producing a photographic transfer image in color accordingto the invention comprises:

(a) treating an imagewise-exposed photographic element, as describedabove, with an alkaline processing composition in the presence of asilver halide developing agent to effect development of each of theexposed silver halide emulsion layers;

(b) the dye-releasing compound then releasing the diffusible azo dye, asdescribed above, imagewise as a function of the development of each ofthe silver halide emulsion layers;

(c) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(d) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

In another preferred embodiment of the invention, a process forproducing a photographic transfer image in color according to theinvention comprises:

(a) treating an imagewise-exposed photographic element as describedabove wherein CAR in the compound has the formula: ##STR19## D, Y, L andj being defined as above, with an alkaline processing composition in thepresence of a silver halide developing agent to effect development ofeach of the exposed silver halide emulsion layers, thereby oxidizing thedeveloping agent;

(b) the oxidized developing agent thereby cross-oxidizing thedye-releasing compound;

(c) the cross-oxidized dye-releasing compound then cleaving as a resultof alkaline hydrolysis to release the diffusible azo dye imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers;

(d) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(e) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

The azo dyes released from the nondiffusible compounds in accordancewith the present invention provide tridentate azo dye ligands that willform coordination complexes in the image-receiving layer with polyvalentmetal ions. The metal ions can be present in the image-receiving layeritself or in a layer adjacent thereto, or the image-receiving layer canbe contacted with metal ions in a bath after diffusion of the dye hastaken place. Metal ions most useful in the invention are those which areessentially colorless when incorporated into the image-receivingelement, are inert with respect to the silver halide layers, reactreadily with the released dye to form a complex of the desired hue, aretightly coordinated to the dye in the complex, have a stable oxidationstate, and form a dye complex which is stable to heat, light andchemical reagents. In general, good results are obtained with polyvalentmetal ions such as copper (II), zinc (II), nickel (II), platinum (II),palladium (II) and cobalt (II) ions.

It is believed that the coordination complex which is formed from thetridentate azo dye ligand according to the invention in one of thepreferred embodiments thereof has the following structure: ##STR20##where Me is metal, Lig is one or more ligand groups depending upon thecoordination number of the metal ion, such as H₂ O, Cl, pyridine, etc;and Z and Z' being defined as above.

In accordance with another embodiment of the invention, a photographicelement is provided which comprises a support having thereon acoordination complex of a polyvalent metal ion and a compound having theformula: ##STR21## wherein G is a metal chelating group, while Z and Z'are defined as above.

The element usually contains a photographic mordant or image-receivinglayer to bind the dye or coordination complex thereto. The structuresshown above may also, of course, be substituted in the same manner asdescribed above for the starting compounds from which they are released.

It will be appreciated that, after processing the photographic elementdescribed above, there remains in the element, after transfer has takenplace, an imagewise distribution of azo dye in addition to developedsilver. A color image comprising residual nondiffusible compound may beobtained in this element if the residual silver and silver halide areremoved by any conventional manner well known to those skilled in thephotographic art, such as a bleach bath followed by a fix bath, ableach-fix bath, etc. Such a retained dye image should normally betreated with metal ions to metallize the dyes to increase their lightfastness and shift their spectral absorption to the intended region. Theimagewise distribution of azo dye may also diffuse out of the elementinto these baths, if desired, rather than to an image-receiving element.If a negative-working silver halide emulsion is employed in certainpreferred photosensitive elements, described above, then a positivecolor image, such as a reflection print, a color transparency or amotion picture film, may be produced in this manner. If adirect-positive silver halide emulsion is employed in suchphotosensitive elements, then a negative color image may be produced.

The photographic element in the above-described process can be treatedwith an alkaline processing composition to effect or initiatedevelopment in any manner. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in thisinvention contains the developing agent for development, although thecomposition could also be solely an alkaline solution where thedeveloper is incorporated in the photographic element, theimage-receiving element or the process sheet, in which case the alkalinesolution serves to activate the incorporated developer.

A photographic film unit which can be processed in accordance with thisinvention is adapted to be processed by passing the unit between a pairof juxtaposed pressure-applying members, such as would be found in acamera designed for in-camera processing, and comprises:

(1) a photogrphic element as described above;

(2) a dye image-receiving layer; and

(3) an alkaline processing composition and means for discharging samewithin the film unit, such as a rupturable container which is adapted tobe positioned during processing of the film unit so that a compressiveforce applied to the container by the pressure-applying members willeffect a discharge of the container's contents within the film unit;

the film unit containing a silver halide developing agent.

In the embodiment described above, the dye image-receiving layer mayitself contain metal ions, or the metal ions may be present in anadjacent layer, so that the tridentate azo dye ligand which is releasedwill form a coordination complex therewith. The dye thus becomesimmobilized in the dye image-receiving layer and metallized at the sametime. Alternatively, the dye image in the dye image-receiving layer maybe treated with a solution containing metal ions to effectmetallization. The formation of the coordination complex shifts theabsorption of the dye to the desired hue, usually to longer wavelengths,which have a different absorption than that of the initial dye-releasingcompound. If this shift is large enough, then the dye-releasing compoundmay be incorporated in a silver halide emulsion layer without adverselyaffecting its sensitivity.

The dye image-receiving layer in the above-described film unit can belocated on a separate support adapted to be superposed on thephotographic element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in U.S. Pat. No.3,362,819. When the means for discharging the processing composition isa rupturable container, is is usually positioned in relation to thephotographic element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as would be found in a typical camera used for in-cameraprocessing, will effect a discharge of the container's contents betweenthe image-receiving element and the outermost layer of the photographicelement. After processing, the dye image-receiving element is separatedfrom the photographic element.

The dye image-receiving layer in the above-described film unit can alsobe located integral with the photographic element between the supportand the lowermost photosensitive silver halide emulsion layer. Oneuseful format for integral receiver-negative photographic elements isdisclosed in Belgian Pat. No. 757,960. In such an embodiment, thesupport for the photographic element is transparent and is coated withan image-receiving layer, a substantially opaque light-reflective layer,e.g., TiO₂, and then the photosensitive layer or layers described above.After exposure of the photographic element, a rupturable containercontaining an alkaline processing composition and an opaque processsheet are brought into superposed position. Pressure-applying members inthe camera rupture the container and spread processing composition overthe photographic element as the film unit is withdrawn from the camera.The processing composition develops each exposed silver halide emulsionlayer, and dye images, formed as a function of development, diffuse tothe image-receiving layer to provide a positive, right-reading imagewhich is viewed through the transparent support on the opaque reflectinglayer background. For other details concerning the format of thisparticular integral film unit, reference is made to the above-mentionedBelgian Pat. No. 757,960.

Another format for integral negative-receiver photographic elements inwhich the present invention can be employed is disclosed in Belgian Pat.No. 757,959. In this embodiment, the support for the photographicelement is transparent and is coated with the image-receiving layer, asubstantially opaque, light-reflective layer and the photosensitivelayer or layers described above. A rupturable container, containing analkaline processing composition and an opacifier, is positioned betweenthe top layer and a transparent cover sheet which has thereon aneutralizing layer and a timing layer. The film unit is placed in acamera, exposed through the transparent cover sheet and then passedthrough a pair of pressure-applying members in the camera as it is beingremoved therefrom. The pressure-applying members rupture the containerand spread processing composition and opacifier over the negativeportion of the film unit to render it light-insensitive. The processingcomposition develops each silver halide layer and dye images, formed asa result of development, diffuse to the image-receiving layer to providea positive, right-reading image which is viewed through the transparentsupport on the opaque reflecting layer background. For further detailsconcerning the format of this particular integral film unit, referenceis made to the above-mentioned Belgian Pat. No. 757,959.

Still other useful integral formats in which this invention can beemployed are described in U.S. Pat. Nos. 3,415,644; 3,415,645;3,415,646; 3,647,437; and 3,635,707. In most of these formats, aphotosensitive silver halide emulsion is coated on an opaque support,and a dye image-receiving layer is located on a separate transparentsupport superposed over the layer outermost from the opaque support. Inaddition, this transparent support also preferably contains aneutralizing layer and a timing layer underneath the dye image-receivinglayer.

Another embodiment of the invention uses the image-reversing techniquedisclosed in British Pat. No. 904,364, page 19, lines 1 through 41. Inthis process, the dye-releasing compounds are used in combination withphysical development nuclei in a nuclei layer contiguous to thephotosensitive silver halide negative emulsion layer. The film unitcontains a silver halide solvent, preferably in a rupturable containerwith the alkaline processing composition.

The film unit or assembly used in the present invention may be used toproduce positive images in single- or multicolors. In a three-colorsystem, each silver halide emulsion layer of the film assembly will haveassociated therewith a dye-releasing compound which releases a dyepossessing a predominant spectral absorption within the region of thevisible spectrum to which said silver halide emulsion is sensitive(initially or after forming the coordination complex), i.e., theblue-sensitive silver halide emulsion layer will have a yellow oryellow-forming dye-releaser associated therewith, the green-sensitivesilver halide emulsion layer will have a magenta or magenta-formingdye-releaser associated therewith, and the red-sensitive silver halideemulsion layer will have a cyan or cyan-forming dye-releaser associatedtherewith, at least one of the dye-releasers being a compound inaccordance with the present invention. The dye-releaser associated witheach silver halide emulsion layer may be contained either in the silverhalide emulsion layer itself or in a layer contiguous to the silverhalide emulsion layer.

The concentration of the dye-releasing compounds that are employed inthe present invention may be varied over a wide range, depending uponthe particular compound employed and the results desired. For example,the dye-releasers of the present invention may be coated in layers byusing coating solutions containing between about 0.5 and about 8 percentby weight of the dye-releaser distributed in a hydrophilic film-formingnatural material or synthetic polymer, such as gelatin, polyvinylalcohol, etc, which is adapted to be permeated by aqueous alkalineprocessing composition.

Depending upon which CAR is used in the present invention, a variety ofsilver halide developing agents can be employed. In certain embodimentsof the invention, any silver halide developing agent can be employed aslong as it cross-oxidizes with the dye-releasers described herein. Thedeveloper may be employed in the photosensitive element to be activatedby the alkaline processing composition. Specific examples of developerswhich can be employed in this invention include:

N-methylaminophenol

Phenidone (1-phenyl-3-pyrazolidone)

Dimezone (1-phenyl-4,4- dimethyl-3-pyrazolidone) aminophenols

1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone

N,N-diethyl-p-phenylenediamine

N,N,N',N'-tetramethyl-p-phenylenediamine

3-methyl-N,N-diethyl-p-phenylenediamine

3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc.

The non-chromogenic developers in this list are preferred, however,since they avoid any propensity of staining the dye image-receivinglayer.

In a preferred embodiment of the invention, the silver halide developeremployed in the process becomes oxidized upon development and reducessilver halide to silver metal. The oxidized developer thencross-oxidizes the dye-releasing compound. The product ofcross-oxidation then undergoes alkaline hydrolysis, thus releasing animagewise distribution of diffusible azo dye which then diffuses to thereceiving layer to provide the dye image. The diffusible moiety istransferable in alkaline processing composition either by virtue of itsself-diffusivity or by its having attached to it one or moresolubilizing groups, for example, a carboxy, sulpho, sulphonamido,hydroxy or morpholino group.

In using the dye-releasing compounds according to the invention whichproduce diffusible dye images as a function of development, eitherconventional negative-working or direct-positive silver halide emulsionsmay be employed. If the silver halide emulsion employed is adirect-positive silver halide emulsion, such as an internal-imageemulsion designed for use in the internal image reversal process, or afogged, direct-positive emulsion such as a solarizing emulsion, which isdevelopable in unexposed areas, a positive image can be obtained incertain embodiments on the dye image-receiving layer. After exposure ofthe film unit, the alkaline processing composition permeates the variouslayers to initiate development of the exposed photosensitive silverhalide emulsion layers. The developing agent present in the film unitdevelops each of the silver halide emulsion layers in the unexposedareas (since the silver halide emulsions are direct-positive ones), thuscausing the developing agent to become oxidized imagewise correspondingto the unexposed areas of the direct-positive silver halide emulsionlayers. The oxidized developing agent then cross-oxidizes thedye-releasing compounds and the oxidized form of the compounds thenundergoes a base-catalyzed reaction to release the dyes imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers. At least a portion of the imagewise distributions of diffusibledyes diffuse to the image-receiving layer to form a positive image ofthe original subject. After being contacted by the alkaline processingcomposition, a pH-lowering layer in the film unit or image-receivingunit lowers the pH of the film unit or image receiver to stabilize theimage.

Internal-image silver halide emulsions useful in this invention aredescribed more fully in the November 1976 edition of ResearchDisclosure, pages 76 through 79, the disclosure of which is herebyincorporated by reference.

The various silver halide emulsion layers of a color film assemblyemployed in this invention can be disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a yellowcolloidal silver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layers for absorbing or filteringblue radiation that may be transmitted through the blue-sensitive layer.If desired, the selectively sensitized silver halide emulsion layers canbe disposed in a different order, e.g., the blue-sensitive layer firstwith respect to the exposure side, followed by the red-sensitive andgreen-sensitive layers.

The rupturable container employed in certain embodiments of thisinvention can be of the type disclosed in U.S. Pat. Nos. 2,543,181;2,643,886; 2,653,732; 2,723,051, 3,056,492; 3,056,491 and 3,152,515. Ingeneral, such containers comprise a rectangular sheet of fluid- andair-impervious material folded longitudinally upon itself to form twowalls which are sealed to one another along their longitudinal and endmargins to form a cavity in which processing solution is contained.

Generally speaking, except where noted otherwise, the silver halideemulsion layers employed in the invention comprise photosensitive silverhalide dispersed in gelatin and are about 0.6 to 6 microns in thickness;the dye-releasers are dispersed in an aqueous alkalinesolution-permeable polymeric binder, such as gelatin, as a separatelayer about 0.2 to 7 microns in thickness; and the alkalinesolution-permeable polymeric interlayers, e.g., gelatin, are about 0.2to 5 microns in thickness. Of course, these thicknesses are approximateonly and can be modified according to the product desired.

Scavengers for oxidized developing agent can be employed in variousinterlayers of the photographic elements of the invention. Suitablematerials are disclosed on page 83 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Any material can be employed as the image-receiving layer in thisinvention as long as the desired function of mordanting or otherwisefixing the dye images is obtained. The particular material chosen will,of course, depend upon the dye to be mordanted. Suitable materials aredisclosed on pages 80 through 82 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Use of a pH-lowering material in the film units employed in thisinvention will usually increase the stability of the transferred image.Generally, the pH-lowering material will effect a reduction in the pH ofthe image layer from about 13 or 14 to at least 11 and preferably 5 to 8within a short time after imbibition. Suitable materials and theirfunctions are disclosed on pages 22 and 23 of the July 1974 edition ofResearch Disclosure, and pages 35 through 37 of the July 1975 edition ofResearch Disclosure, the disclosures of which are hereby incorporated byreference.

A timing or inert spacer layer can be employed in the practice of thisinvention over the pH-lowering layer which "times" or controls the pHreduction as a function of the rate at which the alkaline compositiondiffuses through the inert spacer layer. Examples of such timing layersand their functions are disclosed in the Research Disclosure articlesmentioned in the paragraph above concerning pH-lowering layers.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., alkalimetal hydroxides or carbonates such as sodium hydroxide, sodiumcarbonate or an amine such as diethylamine, preferably possessing a pHin excess of 11, and preferably containing a developing agent asdescribed previously. Suitable materials and addenda frequently added tosuch compositions are disclosed on pages 79 and 80 of the November 1976edition of Research Disclosure, the disclosure of which is herebyincorporated by reference.

While the alkaline processing composition used in this invention can beemployed in a rupturable container, as described previously, toconveniently facilitate the introduction of processing composition intothe film unit, other methods of inserting processing composition intothe film unit could also be employed, e.g., interjecting processingsolution with communicating members similar to hypodermic syringes whichare attached either to a camera or camera cartridge. The processingcomposition may also be applied by means of a swab or by dipping in abath, if so desired.

The alkaline solution-permeable, substantially opaque, light-reflectivelayer employed in certain embodiments of photographic film units used inthis invention are described more fully in the November 1976 edition ofResearch Disclosure, page 82, the disclosure of which is herebyincorporated by reference.

The supports for the photographic elements used in this invention can beany material as long as it does not deleteriously affect thephotographic properties of the film unit and is dimensionally stable.Typical flexible sheet materials are described on page 85 of theNovember 1976 edition of Research Disclosure, the disclosure of which ishereby incorporated by reference.

While the invention has been described with reference to layers ofsilver halide emulsions and dye image-providing materials, dotwisecoating, such as would be obtained using a gravure printing technique,could also be employed. In this technique, small dots of blue-, green-and red-sensitive emulsions have associated therewith, respectively,dots of yellow, magenta and cyan color-providing substances. Afterdevelopment, the transferred dyes would tend to fuse together into acontinuous tone.

The silver halide emulsions useful in this invention, bothnegative-working and direct-positive ones, are well known to thoseskilled in the art and are described in Product Licensing Index, Volume92, December 1971, publication 9232, page 107, paragraph I, "Emulsiontypes"; they may be chemically and spectrally sensitized as described onpage 107, paragraph III, "Chemical sensitization", and pages 108 and109, paragraph XV, "Spectral sensitization", of the above article; theycan be protected against the production of fog and can be stabilizedagainst loss of sensitivity during keeping by employing the materialsdescribed on page 107, paragraph V, "Antifoggants and stabilizers", ofthe above article; they can contain development modifiers, hardeners,and coating aids as described on pages 107 and 108, paragraph IV,"Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII,"Coating aids", of the above article; they and other layers in thephotographic elements used in this invention can contain plasticizers,vehicles and filter dyes described on page 108, paragraph XI,"Plasticizers and lubricants", and paragraph VIII, "Vehicles", and page109, paragraph XVI, "Absorbing and filter dyes", of the above article;they and other layers in the photographic elements used in thisinvention may contain addenda which are incorporated by using theprocedures described on page 109, paragraph XVII, "Methods of addition",of the above article; and they can be coated by using the varioustechniques described on page 109, paragraph XVIII, "Coating procedures",of the above article, the disclosures of which are hereby incorporatedby reference.

The term "nondiffusing" used herein has the meaning commonly applied tothe term in photography and denotes materials that for all practicalpurposes do not migrate or wander through organic colloid layers, suchas gelatin, in the photographic elements of the invention in an alkalinemedium and preferably when processed in a medium having a pH of 11 orgreater. The same meaning is to be attached to the term "immobile". Theterm "diffusible" as applied to the materials of this invention has theconverse meaning and denotes materials having the property of diffusingeffectively through the colloid layers of the photographic elements inan alkaline medium. "Mobile" has the same meaning as "diffusible".

The term "associated therewith" as used herein is intended to mean thatthe materials can be in either the same or different layers so long asthe materials are accessible to one another.

EXAMPLE 1 Preparation of Compound 1

A sample of4-amino-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide(3.43 g; 0.07 mole) was dissolved in 100 ml of methylene chloride undernitrogen andα-(2-benzoyloxy-5-chlorosulfonylphenylazo)-β-benzoyloxycinnamonitrile(3.93 g, 0.07 mole) added portionwise. After the addition was complete,pyridine (1.3 g) was added, and the reaction mixture was allowed to stirat room temperature for 7 hours. The mixture was evaporated to drynessand the residue triturated with ethanol. The product was filtered off,washed with hot ethanol and then purified by dissolving it in hotdimethylformamide and adding ethanol. The product was obtained bychilling the solution. Yield: 4.0 g, m.p. 205° to 207° C.

Intermediatesα-(2-Benzoyloxy-5-chlorosulfonylphenylazo)-β-benzoyloxycinnamonitrile

To a solution ofα-(2-benzoyloxy-5-sulfonylphenylazo)β-benzoyloxycinnamonitrile (10 g) in50 ml of thionyl chloride was added 3 ml of dimethylformamide. Thereaction mixture was allowed to stir at room temperature for 31/2 hours.The solvent was evaporated to dryness under vacuum at room temperature.The residue was diluted with ethyl ether (50 ml) to form a whiteprecipitate. The product was filtered off and dried to yield 9.4 g, m.p.153° to 155° C.

α-(2-Benzoyloxy-5-sulfophenylazo)-β-benzoyloxycinnamonitrile

To a solution of 20 g ofα-(2-hydroxy-5-sulfophenylazo-α-benzoylacetonitrile in 20 ml of drypyridine was added 30 ml of benzoyl chloride. The reaction mixture washeated at reflux for 20 minutes and then cooled to room temperature toform an oily material. The oil material was stirred with 400 ml of ethylether to form a white precipitate. The precipitate was collected byfiltration and dried to yield 11.1 g, m.p. 193° to 195° C.

α-(2-Hydroxy-5-sulfophenylazo-α-benzoylacetonitrile

2-Aminophenol-4-sulfonic acid (18.9 g) was dissolved in aqueous sodiumhydroxide (5 g in 200 ml of water). After the addition of sodium nitrite(7 g), the solution was cooled to 10° C. and added to a mixture ofconcentrated HC1 (25 ml) and 300 g of cracked ice. The diazoniumsolution was stirred at 0° C. for 15 minutes and then added slowly intoa slurry of benzoylacetonitrile (14.5 g), potassium carbonate (30 g) andpyridine (200 ml). When the addition was completed, the reaction mixturewas allowed to stir at 0° C. for 1 hour and then at 20° C. for 1 hour.The solution was acidified with concentrated hydrochloric acid. Theproduct precipitated out after the volume of the reaction mixture wasreduced to 150 ml. The product was filtered off, and dried to yield 17g, m.p. 134 to 137° C.

EXAMPLE 2 Preparation of Compound 2

4-Amino-N,N-didodecyl-1-hydroxy-2-naphthamide (8.07 g) was dissolved in500 ml methylene chloride under nitrogen andα-(2-acetoxy-5-chlorosulfonylphenylazo)acetoacetanilide (6.55 g) addedportionwise. After the addition was complete, pyridine (1.3 g) was addedand the reaction mixture stirred for 5 hours. At the end of this time,most of the starting material had disappeared. The mixture wasevaporated to dryness and the residue triturated with ethanol. Theproduct was filtered off and purified by dissolving it in hotdimethylformamide (50 ml, 80° C.) and adding hot ethanol (400 ml). Thefirst crop of crystals was obtained on chilling. Yield: 8.2 g, m.p. 142to 143° C.

Intermediates α-(2-Acetoxy-5-chlorosulfonylphenylazo)acetoacetanilide

α-(2-Acetoxy-5-sulfophenylazo)acetoacetanilide (20 g) was added tothionyl chloride (100 ml). After the addition of dimethylformamide (4ml), solution was complete, then followed by precipitation of theproduct. It was filtered off and dried in the vacuum oven at 40° C.Yield: 16.7 g, m.p. 225 to 226° C.

α-(2-Acetoxy-5-sulfophenylazo)acetoacetanilide

α-(2-hydroxy-5-sulfophenylazo)acetoacetanilide (40 g) was dissolved inboiling pyridine (750 ml) and acetic anhydride (100 ml) added. Somematerial precipitated while the reaction mixture was hot. After beingcooled, the product was filtered off and dried. Yield: 38 g.

α-(2-Hydroxy-5-sulfophenylazo)acetoacetanilide

b 2-Aminophenol-4-sulfonic acid (18 g) was dissolved in aqueous sodiumhydroxide (5 g in 200 ml of water). After the addition of sodium nitrite(7 g), the solution was cooled to 10° C. and added to a mixture ofconcentrated hydrochloric acid (25 ml) and cracked ice (300 g). Thediazonium solution was stirred at 0° C. for 15 minutes and then addedslowly to a slurry of acetoacetanilide (17 g), potassium carbonate (30g), pyridine (200 ml) and ice. When the addition was complete, thereaction mixture was stirred at 10 to 20° C. for 1 hour and thenacidified with hydrochloric acid. The product was filtered off anddried. Yield: 23 g.

EXAMPLE 3 Photographic Element Tests

Table 1 lists examples of the dye-releasing redox compounds (DRR) ofthis invention. The dyes were prepared as in the previous examples, orby generally analogous methods. Available diffusion hues and lightstability data obtained by the following experiments are recorded.

A. Preparation of Single-Layer Light-Sensitive Elements

The DRR compounds were dispersed in di-n-butyl phthalate in a 1:2 ratio,using cyclohexanone as an auxiliary solvent. The dispersion was added toa monodispersed 0.8 μm silver bromide emulsion and coated on a polyesterfilm support. The layer comprised 2.2 g/m² silver, 3.2 g/m² gelatin and1.1×10⁻³ mole/m² of the DRR compound. It was overcoated by a protectivegelatin layer at 1.1 g/m² containing a conventional gelatin hardener.

B. Dye Diffusion

The above light-sensitive element was exposed to room light. A viscousprocessing composition was spread between it and the receiving elementdescribed below at 22° C. by passing the transparent "sandwich" betweena pair of juxtaposed rollers so that the liquid layer is about 75 μm.The receiving element comprised the following layers coated on atransparent polyester support: (1) a mordant layer containingpoly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammoniumsulfate-co-divinylbenzene) and gelatin, each at 2.2 g/m² ; (2) areflecting layer of titanium dioxide (21.5 g/m²) and gelatin (3.7 g/m²);and (3) an overcoat layer of gelatin (3.8 g/m²). The processingcomposition comprised per liter of aqueous solution: 20 g of sodiumhydroxide 0.75 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone,10 g of potassium bromide and 25 g of hydroxyethylcellulose.

Dye density appearing in the mordant layer was monitored through thetransparent support using a recording reflection densitometer. The dyedensities recorded after 30, 60 and 120 seconds are given in the tableas a percentage of the ultimate final density. High values representrapid transfer to the mordant.

C. Hue

A room light-exposed sample of the above light-sensitive element waslaminated to a transparent receiving element using the same processingcomposition as above. The transparent element comprised a polyestersupport bearing a layer containing the same quaternary ammonium saltcopolymer as above (2.2 g/m²), gelatin (3.2 g/m²) and hardener. When thedye transferred to the sample receivers to a density of about 1.0, theywere washed in water, metallized by bathing in a 10 percent solution ofCuSO₄ ·5H₂ O, washed, soaked in a pH 4 buffer solution and dried. Thesamples which were left unmetallized were simply washed, soaked in thepH 4 buffer and dried. The wavelength at the maximum density (λ_(max))of the spectrophotometric curves is recorded in the table, along withthe "half band width" (1/2 BW), the wavelength range of the curve athalf the maximum density. A narrow "half band width" generallydesignates a pure hue.

D. Light Stability-Fading Test

Sample strips of the light-sensitive element were given a controlledexposure through a step tablet and laminated as described above usingthe same developing composition to a paper receiving element. Thiselement comprised a polyethylene-coated paper support and a mordantlayer of the same composition as on the transparent support in C above.The receivers were metallized, buffered as above and subjected to 10days of a high-density daylight (5000 footcandles) fading. The loss indensity ( ΔD) was monitored spectrophotometrically.

                                      TABLE I                                     __________________________________________________________________________     ##STR22##                                                                                                      Diffusibility                                                                         Hue of                                                                Percent After                                                                         Released Dye                                                                          Chelating                                                                           Light                                                   30 60 120                                                                             λmax                                                                       1/2 BW                                                                            Metal                                                                               Stability             Compound                                                                            CAR    G    G.sup.1 *                                                                           Z      Z' (seconds)                                                                             (nm)                                                                              (nm)                                                                              Me.sup.++                                                                           D.sub.o                                                                          ΔD           __________________________________________________________________________    A     CAR-A OCOCH.sub.3                                                                         OCOCH.sub.3                                                                         CN     C.sub.6 H.sub.5                                                                  -- -- --                                                                              479  82 Cu    1.00                                                                             -0.10              1     CAR-A OCOC.sub.6 H.sub.5                                                                  OCOPh CN     C.sub.6 H.sub.5                                                                  same released dye                           2     CAR-B OCOCH.sub.3                                                                         OH    CONHC.sub.6 H.sub.5                                                                  CH.sub.3                                                                         31 65 88                                                                              470 100 Cu    1.05                                                                             -0.20              B     CAR-A OCOCH.sub.3                                                                         OH    CONHC.sub.6 H.sub.5                                                                  CH.sub.3                                                                         same released dye                           C     CAR-C OCOCH.sub.3                                                                         OH    CONHC.sub.6 H.sub.5                                                                  C.sub.6 H.sub.5                                                                  30 58 87                                                                              440 (broad)                                                                           Cu    1.00                                                                             -0.18              D     CAR-A OCOCH.sub.3                                                                         OH    CONHC.sub.6 H.sub.5                                                                  C.sub.6 H.sub.5                                                                  same released dye                           E     CAR-C OCOCH.sub.3                                                                         OCOCH.sub.3                                                                         CN     CH.sub.3                                                                         47 74 94                                                                              460 100 Cu    0.84                                                                             -0.12              __________________________________________________________________________     *If G.sup.1 is OH, the compound is better represented by the keto rather      than the enol form.                                                           ##STR23##                                                                     ##STR24##                                                                     ##STR25##                                                                

EXAMPLE 4 Released Dyes and Photographic Data

Table 2 lists examples of dyes of the invention which have sulfamoylsubstituents, but which have neither been shifted nor linked todye-releasing carriers. They are the dyes which would be released uponprocessing from sulfonamidonaphthol carriers, like CAR-A of Table 1.

The hue and light stability measurements were made on mordanted stripslike those in Example 3, part C. The dyes were dissolved in an alkalinesolution in which the transparent mordanted strips were soaked until themordant adsorbed a suitable density of dye. The strip was sequentiallywashed, dipped for a few minutes in a concentrated solution of cupricacetate or nickel acetate, washed, soaked in a pH 4.0 buffer solution,washed and dried. Spectrophotometric curves were measured both beforeand after 2 days of the high-intensity daylight fading test. Theoriginal density at λ_(max) and the loss on fading are recorded in thetable.

                                      TABLE 2                                     __________________________________________________________________________     ##STR26##                                                                                       Hue of Dye                                                                            Chelating                                                                           Light                                                           λmax                                                                       1/2 BW                                                                            Metal Ion                                                                           Stability                                    Compound                                                                            Z'  Z        (nm)                                                                              (nm)                                                                              Me.sup.++                                                                           D.sub.o                                                                          ΔD                                  __________________________________________________________________________    F     CH.sub.3                                                                          CO.sub.2 H                                                                             440 93  Cu    1.13                                                                             0.03                                      G     CH.sub.3                                                                          CONH.sub.2                                                                             430 82  Cu    1.39                                                                             0.05                                      H     C.sub.6 H.sub.5                                                                   CONHC.sub.6 H.sub.5                                                                    448 94  Cu    1.28                                                                             0.03                                      J     CH.sub.3                                                                          CN       452 78  Cu    1.33                                                                             0                                                            462 76  Ni    1.36                                                                             0.03                                      K     C.sub.6 H.sub.5                                                                   SO.sub.2 CH.sub.3                                                                      441 110 Cu    1.18                                                                             0.07                                      L     nC.sub.4 H.sub.9                                                                  CN       450 72  Cu    1.10                                                                             0                                         __________________________________________________________________________

EXAMPLE 5 Preparation of Compound 8

A sample of α-(2-hydroxy-5-sulfamoylphenylazo)-acetoacetonitrile (2.80g; 0.01 mole) was dissolved in dried pyridine (50 ml).2,5-Didodecyl-3,6-bis(N-methylchloroformamidomethyl)benzoquinone (3.3 g,0.005 mole) was added gradually to the pyridine solution and the mixturewas allowed to react for two hours at room temperature. The reactionmixture was poured onto ice, acidified and filtered to obtain 5 g ofcrude product. The crude product was dissolved in a minimum amount ofdichloromethane and chromatographed on silica gel using a mixed solvent(ethanol/dichloro-methane, 2:98) as the eluting agent. The first yellowfraction was discarded. The second fraction was concentrated to obtain2.9 g of product (ε=3.3×10⁴ at 365 nm).

Intermediates Sodium salt of acetoacetonitrile

A solution of sodium methoxide (4.8 g) in absolute ethanol (25 ml) wasadded gradually to a solution of 5-methylisoxazole (3.4 g) in ethanol(30 ml) at ice bath temperature. The mixture was maintained at 0° C. for30 minutes and then diluted with anhydrous ethyl ether (150 ml) toprecipitate the sodium salt of acetoacetonitrile. After filtration ofthe mixture, the white precipitate was dissolved in distilled water (50ml) and treated with a cooled solution of potassium carbonate (24.0 g)in ice (50 g).

2-Hydroxy-5-sulfamoylbenzenediazonium chloride

Sodium nitrite (3.5 g) was added to a solution of2-amino-5-sulfamoyl-1-phenol (5.6 g) in aqueous sodium hydroxide (1.6 gNaOH, 50 ml H₂ O). Concentrated hydrochloric acid (10 ml) was addeddropwise to this solution at 0° C. for 15 minutes with stirring.

α-(2-Hydroxy-5-sulfamoylphenylazo)acetoacetonitrile

The diazonium salt solution was added to the acetoacetonitrile solution,and the resulting mixture was maintained at 0° C. for 15 minutes andthen at room temperature for 60 minutes.

The solution was acidified with concentrated hydrochloric acid andmaintained at 0° C. to obtain a yellow precipitate which was collectedby filtration and dried; yield, 6.5 g.

Example 6 Preparation of Compound 10 SOLUTION A (Sodium salt ofacetoacetonitrile)

A solution of sodium methoxide (10.4 g) in absolute ethanol (80 ml) wasadded dropwise to the solution of 5-methylisozazole (6.8 g) and absoluteethanol (30 ml) maintained in an ice ethanol bath. After 30 minutes, awhite precipitate gradually formed; after dilution with ethyl ether (800ml) and filtration, the white precipitate was re-suspended in a mixtureof methanol (900 ml) and sodium acetate (212 g) maintained in an icebath.

SOLUTION B (Diazonium salt)

4-(3-Amino-4-hydroxybenzenesulfonamido)-N-[4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-2-naphthamide(26.4 g) was dissolved in ethanol (400 ml) and treated with a methanolsolution (200 ml) of hydrochloride gas (16.8 g). Isopentyl nitrite (5.7g) was added dropwise to this mixture at 0° C. After completion of theaddition, the reaction mixture was maintained at 0° C. for 30 minutes.

Solution B was added very slowly to Solution A at 0° C. whilemaintaining the vessel's contents at a basic pH with sodium acetate.After maintaining the mixture at 0° C. for 30 minutes, the reactionvessel was allowed to stand at room temperature for 60 minutes. Thesolution was acidified with methanol/hydrogen chloride to pH 6.0. Thereaction mixture was concentrated to 500 ml in vacuo and filtered toremove sodium chloride and unreacted sodium acetate. The filtrate wasconcentrated to an oil which, after treating with distilled water (1liter) for 15 hours, formed a yellow precipitate which was collected byfiltration and dried; yield, 26.0 g.

The crude product was re-dissolved in ethyl ether and allowed to standfor 10 minutes at room temperature to form a jelly material which wasremoved by filtration; the filtrate was concentrated to dryness to yielda solid which was purified by liquid column chromatography using silicagel and a mixture of methanol and dichloromethane (1.5:98.5) as aneluting agent; yield, 11.0 pure compound.

EXAMPLE 7 Photographic Test -- Compound 8

A single-color photosensitive element was prepared by coating on asubbed polyester film support (g/m² in parentheses unless otherwisespecified). (1) a blue-sensitive 0.8 μm monodispersed silver bromidegelatin emulsion (1.1 Ag, 3.2 gelatin) and a dispersion of a mixture of(a) Compound 8 (0.51) and (b) a ballasted reducing agent precursor4-(2-acetoxy-2-pivaloylacetamido)-N-[4-(2,4-di-t-pentylphenoxy)-butyl]-1-hydroxy-2-naphthamide(1.02) dissolved in diethyl-lauramide (1.53), and (2) an overcoat layerof gelatin (0.55). This element was exposed through a graduated densitystep tablet to a light source. It was then processed by spreadingbetween it and an image-receiving element at 22° C. a viscous developingcomposition by passing the transfer "sandwich" between a pair ofjuxtaposed rollers so that the liquid layer was 75 μm. The receivingelement comprised a layer of a mixture of gelatin (2.15) and a polymericlatex mordant,poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammoniumsulfate-co-divinylbenzene) (2.15) coated on a polyethylene-coated papersupport. The viscous composition contained (per liter of water) 51 g ofpotassium hydroxide, 3 g of4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 20 g of potassiumbromide, 1.0 g of 5-methylbenzotriazole and 30 g ofcarboxymethylcellulose.

After 5 minutes, the elements were peeled apart and the receivingelement was washed in water and dried. The D_(max) and D_(min) of theyellowish unmetallized dye, read using blue light reflectiondensitometry, was 0.85 and 0.20, respectively. Metallized withnickel(II) and copper(II) ions, the dye absorbed at λ_(max) 462 and 450nm, respectively.

EXAMPLE 8 Photographic Test -- Compound 10

A single-color integral-imaging receiver element was prepared by coatingsuccessively on a polyester film support (1) a metallizing layercomprising gelatin (1.08 g/m²) and nickel sulfate hexahydrate (0.58g/m²), (2) a receiving layer comprising a mixture of gelatin andpoly(4-vinylpyridine), (each at 2.15 g/m²), (3) a reflecting layercomprising titanium dioxide and gelatin in a 6.25/1 ratio, (4) an opaquelayer of carbon dispersed in gelatin, (5) a layer ofdidodecylhydroquinone (1.29 g/m²) dispersed in gelatin (1.61 g/m²), (6)a layer comprising gelatin (2.13 g/m²), and a dispersion of Compound 10(0.95 g/m²), (7) a layer of a blue-sensitized internal image emulsion,as described in Evans, U.S. Pat. No. 3,761,276 (1.85 gAg/m², 1.85 ggelatin/m²), with fogging agents NA-16 and H-25 of Leone et al, U.S.Pat. No. 4,030,925, issued June 21, 1977, and5-octadecylhydroquinone-2-sulfonic acid (16 g/mole Ag), and (8) agelatin overcoat layer (0.89 g/m²).

In a comparative coating in which no metal ion is used to chelate thedye, the entire layer 1 was omitted. Layers 1 and 2 above form no partof the invention, as they are the subject of an invention by ourcoworkers Brust, Hamilton and Wilkes, U.S. application Ser. No. 003,169,filed Jan. 15, 1979.

This integral element was exposed to a multicolor test object, thenprocessed by spreading between it and a processing cover sheet, asdescribed in Hannie et al, U.S. Pat. No. 4,061,496, at 22° C., a viscousprocessing composition, as described in said U.S. Pat. No. 4,061,496, bypassing the transfer "sandwich" between a pair of juxtaposed rollers sothat the liquid layer was about 75 μm. The dye reflection density in theunexposed areas (i.e., D_(max) areas) was measured at selected intervalsup to 24 hours after a recording spectrophotometer. The density atλ_(max) after 4 minutes was determined from these plots. From thespectrophotometric curves, the final D_(max) and the λ_(max) (i.e.,wavelength at D_(max)) were determined and recorded in Table 3. Thelight stability was determined by exposing part of the strip to a highintensity daylight (5000 footcandles) light source for two days. Valuesare given for the original density D_(o), the final faded density D_(f)and the density loss ΔD.

                  TABLE 3                                                         ______________________________________                                                λ.sub.max                                                                      Light Stability                                               Metallization                                                                           (nm)      D.sub.o  D.sub.F 66 D                                     ______________________________________                                        Ni.sup.++ 467       1.00     0.91    -0.09                                    None (H)  <400      1.00     0.54    -0.46                                    ______________________________________                                    

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be appreciated thatvariations and modifications can be effected within the spirit and scopeof the invention.

What is claimed is:
 1. A photographic element comprising a supporthaving thereon a layer comprising a photographic mordant having boundthereto a coordination complex of a polyvalent metal ion and a compoundhaving the following formula: ##STR27## wherein: G is a metal chelatinggroup;Z is an electron withdrawing group having the formula --CON(R)₂,--SO₂ N(R)₂, --COOR, --CN, SO₂ R' or --COR', wherein R' is an alkylgroup of 1 to 8 carbon atoms or an aryl group of 6 to 10 carbon atoms,and each R is H or R'; and Z' is an alkyl group of 1 to 8 carbon atoms,an aryl group of 6 to 10 carbon atoms or N(R)₂.
 2. The photographicelement of claim 1 wherein the metal ion is nickel (II), copper (II),zinc (II), platinum (II), palladium (II) or cobalt (II).